CN101462738A - Method for synthesizing high silicon beta zeolite - Google Patents
Method for synthesizing high silicon beta zeolite Download PDFInfo
- Publication number
- CN101462738A CN101462738A CNA2008102469831A CN200810246983A CN101462738A CN 101462738 A CN101462738 A CN 101462738A CN A2008102469831 A CNA2008102469831 A CN A2008102469831A CN 200810246983 A CN200810246983 A CN 200810246983A CN 101462738 A CN101462738 A CN 101462738A
- Authority
- CN
- China
- Prior art keywords
- sio
- beta zeolite
- gel
- silicon
- mol ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 96
- 239000010703 silicon Substances 0.000 title claims abstract description 96
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 92
- 239000010457 zeolite Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 58
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 90
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 238000002425 crystallisation Methods 0.000 claims description 40
- 230000008025 crystallization Effects 0.000 claims description 39
- 239000006229 carbon black Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 12
- 238000010907 mechanical stirring Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011737 fluorine Substances 0.000 abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 abstract description 7
- 239000002808 molecular sieve Substances 0.000 abstract description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000005216 hydrothermal crystallization Methods 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 17
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 16
- 235000019241 carbon black Nutrition 0.000 description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 10
- 239000003292 glue Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 9
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 229960002050 hydrofluoric acid Drugs 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 3
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000009992 mercerising Methods 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- -1 1-benzyl-1-methyl-cyclohexyl Chemical group 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910021418 black silicon Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- LNIYNESXCOYFPW-UHFFFAOYSA-N dibenzyl(dimethyl)azanium Chemical compound C=1C=CC=CC=1C[N+](C)(C)CC1=CC=CC=C1 LNIYNESXCOYFPW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- PTMFUWGXPRYYMC-UHFFFAOYSA-N triethylazanium;formate Chemical compound OC=O.CCN(CC)CC PTMFUWGXPRYYMC-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a technique for synthesizing aluminosilicate zeolite molecular sieves, in particular to a method suitable for synthesizing high-silicon beta zeolite by using a fluorine-containing hydrothermal system on an industrial scale. The method has the main technical characteristic of using an ethanol solvent to disperse subacid fluorine-containing gel so as to reduce the hardness of the gel and provide convenience for crystallizing beta zeolite under a stirring condition. The method is beneficial to the hydrothermal crystallization of fluorine-containing gel in a large-scale industrial synthesis kettle. The ethanol solvent is safe, cheap, friendly to environment and easy to recycle.
Description
Technical field
The present invention relates to aluminosilicate zeolite molecular sieve synthetic technology, be specifically related to a kind of method that is suitable on technical scale, using fluorinated water hot system synthesizing high silicon beta zeolite.
Background technology
The beta zeolite be by U.S. Mobil company in 1967 with hydrothermal crystallization method synthetic (USP308069) first in tetraethyl ammonium hydroxide strong basicity system.Because of having 12 yuan of ring intersection pore passage structures of unique three-dimensional and good thermostability, hydrothermal stability, the beta zeolite shows excellent catalytic performance as catalyzer in refining of petroleum such as hydrocracking, hysomer, dewaxing, alkylating aromatic hydrocarbon, olefin hydration and petrochemical process, be a kind of important industrial zeolite molecular sieve.
On topological framework, beta zeolite and M (mercerising), ZSM-12 zeolite belong to same family.When in the strong alkaline water hot system of routine, synthesizing the beta zeolite, silica alumina ratio (SiO
2/ Al
2O
3Mol ratio) scope is very limited.This is (as, SiO because during synthesizing low silicon aluminum ratio beta zeolite
2/ Al
2O
3Mol ratio is lower than 30) produce M (mercerising) stray crystal through regular meeting, and during synthesizing high-silicon aluminum ratio beta zeolite (as, SiO
2/ Al
2O
3Mol ratio is higher than 60, particularly 100-∞) produce ZSM-12 zeolite and ZSM-5 zeolite stray crystal through regular meeting.The beta zeolite of low silica-alumina ratio has high reactivity as solid acid catalyst.The beta zeolite of high silica alumina ratio or total silicon also has a lot of potential application as the carrier or the sorbent material of metal load type catalyst etc.
The 1980s, Europatent (application number 83302773.3, publication number EP0095303A1; Application number 83302774, publication number EP0094827B1), United States Patent (USP) (application number 06606499, publication number US4554065) proposed to improve the method for beta zeolite silica alumina ratio by the mineral acid dealuminzation, yet for industrial application, directly obtaining high silicon or total silicon beta zeolite with hydrothermal synthesis method can reduce production costs, and avoids the pollution of mineral acid discharging to environment, has tangible practical value.
Therefore, in middle 1990s, open source literature (J.Chem.Soc., Chem.Commun., 1994,1241) and (Chem.Commun., 1996,1339) reported with the beta zeolite that takes off boron or dealuminzation and done the directly method of synthetic total silicon beta zeolite of crystal seed.Afterwards, people had reported the method for the synthetic total silicon beta zeolite of direct hydro-thermal in succession in patent documentation and open source literature.For example:
U.S.'s patent of invention (application number 40437, publication number US4923690) has disclosed a kind of method of direct hydro-thermal synthesizing high silicon beta zeolite.Its technical characterictic is, is the silicon source with white carbon black or silica gel, is the aluminium source with the sodium aluminate, with the tetraethylammonium cation is template, optionally adds sodium-chlor, in 90-200 ℃ of following crystallization, the silica alumina ratio that gets is 20-1000, and relative crystallinity is the beta zeolite of 30%-90%.When silica alumina ratio raise, degree of crystallinity descended, and crystallization is incomplete.
U.S.'s patent of invention (application number 07715190, publication number US5164169) has disclosed a kind of method of direct hydro-thermal synthesizing high silicon beta zeolite.Its technical characterictic is, with the white carbon black is the silicon source, and sodium aluminate is the aluminium source, with sequestrant such as trolamine and tetraethyl ammonium ionization as template, add highly purified beta crystal seed in 70-175 ℃ of following crystallization, can obtain silica alumina ratio is the higher beta zeolite of 200-1000 and purity.
Chinese invention patent (application number 93117594.1, publication number CN1086793A) has disclosed the method for the synthetic beta zeolite of a kind of direct hydro-thermal.Its technical characterictic is, is the silicon source with water glass, and tetraethyl ammonium hydroxide is a template, and adds yellow soda ash, is 3.3SiO in the batching mol ratio
2: 0.22 (TEA)
2O:1.0Na
2O:36H
2O:0.33Na
2CO
3Situation under, in 140 ℃ of following crystallization 30 hours, what obtain was that silica alumina ratio is 19.1 beta zeolite with static still.Though it should be noted that batching SiO
2/ Al
2O
3=∞, but total silicon or high silicon beta zeolite do not synthesized.
Reported the method for the synthetic total silicon beta zeolite of a kind of direct hydro-thermal among open source literature Micropor.Mesopor.Mater.28 (1999) 519-530.Its technical characterictic is, is the silicon source with the white carbon black, and with 4, the non-corresponding isomer of two (1-benzyl-1-methyl piperidine) quaternary ammonium salt cationics of 4 '-trimethylene is a structure directing agent, is (0.05-0.15) SDA at feed ratio
2+(OH-)
2/ SiO
2/ 50H
2Under the condition of O, synthesized total silicon beta zeolite at 135-150 ℃ of following crystallization 2-16 days with leaving standstill still.The template complicated process of preparation that relates in this method.
Open source literature Chem.Commun., 2001, reported the method for the synthetic total silicon beta zeolite of a kind of direct hydro-thermal among the 1486-1487.Its technical characterictic is, is the silicon source with positive tetraethyl orthosilicate, is template (that is, a N-methyl quaternary ammonium hydroxide of triethylene diamine) with DABMe (OH), and 150 ℃ of following crystallization 12 days, hydro-thermal synthesized total silicon beta zeolite.Equally, the template that relates in this method is very expensive.
Reported the method for the synthetic total silicon beta zeolite of a kind of direct hydro-thermal among open source literature Micropor.Mesopor.Mater.90 (2006) 237-245.Its technical characterictic is, is silicon source (containing sodium, self-control) with the solid silicone, and tetraethyl ammonium hydroxide is a template, is 0.35Na in the batching mol ratio
2O:4.5 (TEA)
2O:25SiO
2: 295H
2Under the situation of O, aged at room temperature 24 hours stirred crystallization 11 days subsequently in stirring tank, obtain total silicon beta zeolite.
Reported a kind of method of direct hydro-thermal synthesizing high silicon beta zeolite in the open source literature (the metallurgical .2007 in Shandong, 29:(6)).Its technical characterictic is, is the silicon source with silica gel, and sodium aluminate is the aluminium source, and tetraethylammonium bromide is a template, and adds sodium hydroxide, and with leaving standstill still in 140-150 ℃ of following crystallization 40 hours, obtaining silica alumina ratio is the beta zeolite of 40-248.
Open source literature Acta Phys.-Chim.Sin.2008,24 (7): the method for having reported a kind of direct hydro-thermal synthesizing high silicon beta zeolite among the 1192-1198.Its technical characterictic is, is the silicon source with silica gel, and sodium aluminate is the aluminium source, and tetraethyl ammonium hydroxide is a template, and the batching mol ratio is (0.002-0.03) Al
2O
3: SiO
2: (0.03-0.1) (TEA)
2OH:(0.05-0.28) Na
2O:(3.4-8.0) H
2O is the beta zeolite of 24-452 with leaving standstill still in 120-180 ℃ of following crystallization 12-32 hour, obtaining the silica alumina ratio scope.
The synthetic method of above patent and open source literature introduction is because of carrying out the directly synthetic of total silicon or high silicon beta zeolite in the strong basicity environment, be difficult to avoid ZSM-12 or/and ZSM-5 zeolite stray crystal, and have the low problem of zeolite product yield; The method that has requires to use the special template agent, and it prepares difficulty, costs an arm and a leg, and is unfavorable for industrial production.
Also reported the method for synthetic total silicon of the direct hydro-thermal of fluorine-containing system or high silicon beta zeolite in following patent documentation and the open source literature.For example:
Chinese invention patent (application number 00131432.7, publication number CN1096417C) has disclosed the method for the synthetic total silicon beta zeolite of a kind of direct hydro-thermal.Its technical characterictic is, is the silicon source with water glass, and tetraethyl ammonium hydroxide is a template, add concentrated hydrochloric acid and add sodium hydroxide and Neutral ammonium fluoride simultaneously, and be SiO in the batching mol ratio
2: 0.25TEA:0.32Na
2O:0.15F:12.0H
2Under the situation of O, with leaving standstill still in 80 ℃ of down aging 24h, in 150 ℃ of following crystallization 4 days, the total silicon beta zeolite that obtains.But its degree of crystallinity is lower.
Chinese invention patent application number 200710099567.9 (publication number CN101311116A) has disclosed the method for the synthetic full-silicon beta zeolite of a kind of direct hydro-thermal.Its technical characterictic is, is the silicon source with the self-control silica gel particle, and tetraethyl ammonium fluoride (or the tetraethyl ammonium compound except that tetraethyl ammonium fluoride and the mixture of fluorochemical) is a template, and the batching mol ratio is SiO
2: H (0.1-1) TEA:(1.0-8.0)
2O, with under the 100-190 ℃ of temperature crystallization 1-7 days, the full-silicon beta zeolite that obtains had nano-scale in leaving standstill still.Wherein, silica gel particle is according to the organosilicon acid esters: hydrolytic reagent: water=1.0:(0.001-0.080): mol ratio (2.0-15.0), with organic amine, organic acid or mineral acid as hydrolytic reagent, be added to the water jointly with the organosilicon acid esters and fully stir, at pH is 3-14, temperature grinds to form silica gel particle for obtaining the silicon gel in ageing 0.3-48 hour under-20-100 ℃ the condition behind the silicon gel drying with gained.This method silicon source preparation process complexity, and template costliness.
Open source literature Chem.Commun., 1996,2365., reported the method for the synthetic total silicon beta zeolite of a kind of direct hydro-thermal among Micropor.Mesopor.Mater.22 (1998) 1-8 and Micropor.Mesopor.Mater.46 (2001) 35-46.Its technical characterictic is, is the silicon source with the tetraethoxy, and tetraethyl ammonium hydroxide is a template, and hydrofluoric acid is mineralizer, is 0.54TEAOH:0.54HF:SiO in the batching mol ratio
2: 7.25 H
2O, crystallization temperature are 140 ℃, and stirring velocity and crystallization time are respectively under the condition of 60rpm and 39 hours and synthesize the beta zeolite that grain size is the 0.5-5 micron.But the gel with above-mentioned feed ratio preparation is a white solid, has increased great difficulty for the mechanical stirring operation in the building-up process.
Open source literature Topics in Catalysis 9 (1999) 59-76 have reported the method for synthetic total silicon of a kind of direct hydro-thermal and high silicon beta zeolite.Its technical characterictic is, is the silicon source with the tetraethoxy, and the derivative of tetraethyl ammonium hydroxide or triethylene diamine is a template, is mineralizer with fluoric acid or Neutral ammonium fluoride, and the batching mol ratio is 0.5SDAOH:0.54HF:SiO
2: 7.5H
2O, the stirring velocity with 60rpm under 140-175 ℃ stirred crystallization 2.5-14 days, and hydro-thermal synthesizes full-silicon beta zeolite.
Reported a kind of method of directly synthetic total silicon beta zeolite among open source literature Catalysis Today 74 (2002) 271-279.Its technical characterictic is, is the silicon source with positive tetraethyl orthosilicate, and with 1,4-diazabicyclo [2.2.2] octane is template and adds HF, is SiO in the batching mol ratio
2: 0.25SDAOH:0.5HF:10H
2O, the rotating speed with 66rpm under 150 ℃ stirred crystallization 14-30 days, obtained the beta zeolite of total silicon.Employed template preparation difficulty costs an arm and a leg in this method.
Reported a kind of method of directly synthetic total silicon beta zeolite in the open source literature (chemical journal .2002,60:(3)).Its technical characterictic is, is the silicon source with the tetraethoxy, and tetraethyl ammonium hydroxide is a template, and hydrofluoric acid is mineralizer, is 1.0SiO in the batching mol ratio
2: 0.54TEAOH:0.54HF:10H
2Under the condition of O and adding beta zeolite seed crystal,, obtain total silicon beta zeolite in 130-140 ℃ time static crystallization 4-5 days.The template of using in this method is relatively inexpensive to be easy to get, but does not see the report of industrial application.
Open source literature Studies in Surface Science and Catalysis, 154 (2004) 725-730 and Chem.Mater.2004.4 (17): reported the synthetic total silicon beta zeolite of two step crystallization method hydro-thermals among the 725-730.Its technical characterictic is that (1) forms the beta nucleus with fluorine-containing system when the approaching neutrality of pH; (2) in gel, produce the pH value that improves system under the situation of nucleus and impelled nucleus growth.It with the white carbon black silicon source, tetraethyl ammonium hydroxide and tetraethyl ammonium fluoride are template, and add sodium hydroxide, potassium hydroxide, or Sodium Fluoride, Potassium monofluoride, the batching mol ratio is (0-0.3) TEAOH:(0.3-0.5) TEAF:(0-0.1) NaF:(0-0.05) KF:(0-0.1) NaOH:(0-0.05) KOH:SiO
2: (5-13.8) H
2Under the situation of O, in 140-150 ℃ of crystallization 4-22 days, synthesize total silicon beta zeolite in leaving standstill still, its grain size is the 2-15 micron.The template of using in this method is also relatively inexpensive to be easy to get, but the operation of online adjustment system potential of hydrogen (pH value) is very difficult after the first step forms the zeolite nucleus, does not see the report of industrial application.
Open source literature Chem.Mater.2005,17, reported a kind of method of directly synthesizing total silicon beta zeolite among the 4374-4385.Its technical characterictic is, is the silicon source with the tetraethoxy, and dibenzyl Dimethyl Ammonium positively charged ion is a structure directing agent, is 0.54SDAOH:(0-0.26 in the batching mol ratio) SDACl:0.54HF:SiO
2: (4.6-7.93) under the situation of H20, with leaving standstill still in 135 ℃ of following crystallization 7-45 days, synthesize total silicon beta zeolite, its grain size is the 2-32 micron.The template of using in this method is also relatively inexpensive to be easy to get, but does not see the report of industrial application.
Reported the method for synthetic total silicon of a kind of direct hydro-thermal and high silicon beta zeolite among open source literature Micropor.Mesopor.Mater.89 (2006) 88-95.Its technical characterictic is, is the silicon source with the white carbon black, and tetraethyl ammonium hydroxide is a template, as mineralizer, optionally adds sodium hydroxide with Neutral ammonium fluoride, is (0.25-0.45) TEAOH:(0.4-0.45 in the batching mol ratio) NH
4F:(0-0.2) NaOH:SiO
2: (4.5-6.33) H
2O, with leaving standstill still in 140 ℃ of following crystallization 6-16 days, having obtained grain size is the total silicon beta zeolite of 10-15 micron.This method does not have the industrialization report yet.
Reported the method for the synthetic total silicon beta zeolite of a kind of direct hydro-thermal among open source literature Micropor.Mesopor.Mater.89 (2006) 235-245.Its technical characterictic is, is the silicon source with the tetraethoxy, is structure directing agent with 1-benzyl-1-methyl-cyclohexyl amine (BMHM) and fluorine-containing derivant thereof, is (0.44-0.54) SDAOH:0.54HF:SiO in the batching mol ratio
2: (4.55-7.93) H
2Under the situation of O,, synthesize total silicon beta zeolite with leaving standstill still in 135-150 ℃ of following crystallization 7-63 days.The template that relates in this method is difficult to obtain, and costs an arm and a leg, and not seeing has the industrial application report.
Open source literature Angew.Chem.Int.Ed.2006,45,8013-8015 and Chem.Mater.2008,20, reported the method for the synthetic total silicon beta zeolite of a kind of direct hydro-thermal among the 3218-3223.Its technical characterictic is that with 4,4-dimethyl-4-nitrogen father-in-law three ring [5.2.2.0] 11 carbon-8-alkene are structure directing agent.Adding KOH and NH
4When F is mineralizer, in leaving standstill still,, obtain total silicon beta zeolite in 175 ℃ of following crystallization 14 days.The template that relates in this method is difficult to obtain, and costs an arm and a leg, and does not have the report of industrial application at present.
Reported the method for the synthetic total silicon beta zeolite of a kind of direct hydro-thermal among open source literature Micropor.Mesopor.Mater.93 (2006) 55-61.Its technical characterictic is, with white carbon black and TEA
2SiF
6Be the silicon source, (TEA wherein
2SiF
6By (NH
4)
2SiF
6Be dissolved among the TEAOH obtained), tetraethyl ammonium hydroxide is a template, is mineralizer with potassium hydroxide, is 1.0SiO in the batching mol ratio
2: TEA KOH:(0.5-0.9 (0.3-0.4) TEAOH:(0-0.1))
2SiF
6: (6.5-7.8) H
2Under the situation of O, wore out 24 hours down in 25 ℃,, synthesize total silicon beta zeolite, still do not have the report of industrial application in 150 ℃ of following crystallization 7-23 days with leaving standstill still.
Open source literature Micropor.Mesopor.Mater. has reported the method for synthetic total silicon of a kind of direct hydro-thermal and high silicon beta zeolite among 100 (2007) 118-127.Its technical characterictic is, is the silicon source with the white carbon black, and tetraethyl ammonium hydroxide and methylamine are template, and hydrofluoric acid is mineralizer, is 10SiO in the batching mol ratio
2: 1.5HF:5TEAOH:5CH
3NH
2: 100H
2Under the situation of O,, synthesize total silicon beta zeolite with leaving standstill still in 140 ℃ of following crystallization 15 days.When adding aluminium hydroxide in the system, can synthesize the high silicon beta zeolite of Si/Al than (mole)=5400.This method does not have the report of industrial application at present.
Reported the method for the synthetic total silicon beta zeolite of a kind of direct hydro-thermal in the open source literature (applied chemistry .2007,24:(7)).Its technical characterictic is, is the silicon source with the white carbon black, and tetraethyl ammonium hydroxide is a template, and Sodium Fluoride is a mineralizer, is 60SiO in the batching mol ratio
2: (17-18) (TEA)
2OH:(5-40) H NaF:(480-660)
2Under the situation of O,, synthesize total silicon beta zeolite with leaving standstill still in 140 ℃ of following crystallization 12 days.But the report that does not have industrial application.
There are following problem in direct hydro-thermal synthesizing high-silicon of above-mentioned fluorine-containing system or total silicon beta zeolite method: used the special template agent in the method that has; Because a large amount of Neutral ammonium fluorides of employing are mineralizer, cause the gel of being prepared no longer to be alkalescence, but be slightly acidic in all the other methods.We find through experiment, and this to have a weakly acidic Silicon-rich gel hardness very big, is difficult to carry out mechanical stirring, and this gives and adopts large-scale hydrothermal crystallizing still to carry out synthetic production of mass-producing to have caused difficulty.Because in large-scale hydrothermal crystallizing still,, will make the very big thermograde of existence in the gel, thereby cause the inhomogeneous and failure of crystallization if can not effectively stir to gel.We attempted recently reducing gel hardness by increasing water silicon.But, amount of water hour DeGrain, and amount of water can cause crystallization rate to reduce greatly when big.
Summary of the invention
The purpose of this invention is to provide a kind of novel method, it can reduce the hardness of the fluoride gel that is used for direct hydro-thermal synthesizing high-silicon or total silicon beta zeolite, and the synthetic beta zeolite of fluoride gel system can be carried out in the hydrothermal crystallizing still of mass-producing.We find that through screening study this purpose can realize by gelatigenous way in alcohol solvent.In fact, other alcohols such as methyl alcohol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, ethylene glycol, propylene glycol, 1, the 3-butyleneglycol, glycerol, and higher alcohols such as n-Octanol etc. all have similar effect, and except alcohols, organic solvent such as thanomin, polyvinyl alcohol, acetone, polyvinyl lactam and soil temperature compound and tensio-active agent also have certain similar effect.
But for other organism, the alcoholic acid advantage is low price, safety non-toxic, recycling use easily.And adopt alcohol solvent both can effectively reduce the hardness of the fluoride gel of synthetic total silicon or high silicon beta zeolite, can avoid again beta zeolite crystallization process is produced big influence.Can adopt dehydrated alcohol in the actual production, also can adopt 95% industrial spirit.Should in prescription, be adjusted by the moisture that the industrial spirit solvent is brought into.
Technical scheme of the present invention is: white carbon black is the silicon source, and aluminum hydroxide solid elastomer is the aluminium source, and TEAOH solution is template.Earlier alcohol solvent and TEAOH template solution are joined in the material-compound tank successively by following mol ratio, under agitation add white carbon black and aluminum hydroxide solid elastomer then and mix, in the gained feed liquid, add solid NH again
4F, the mol ratio of each material is:
SiO
2/Al
2O
3＝100-∞，
(TEA)O
2/SiO
2＝0.2-0.4，
OH
-/SiO
2＝0.4-0.8，
NH
4F/SiO
2＝0.25-0.5，
H
2O/SiO
2＝5.0-15，
CH
3CH
2OH/SiO
2＝0.5-100，
Continue to stir up to forming the homogeneous gel mixture, gel mixture is moved in the stainless steel high pressure crystallizing kettle, 140-160 ℃ of following mechanical stirring crystallization 2-30 days.
Described alcohol solvent is industry anhydrous ethanol or contains 95% alcoholic acid industrial spirit.
The invention has the beneficial effects as follows: be scattered in the alcohol solvent by the high rigidity fluoride gel that will synthesize total silicon or high silicon beta zeolite; improved the mechanical stirring performance of gel, made fluoride gel in the industrial synthesis reactor of mass-producing, become total silicon or high silicon beta zeolite by hydrothermal crystallizing.For other organism such as alcohols that similar effect is arranged, adopt alcohol solvent both can effectively reduce the hardness of the fluoride gel of synthetic total silicon or high silicon beta zeolite, can avoid again beta zeolite crystallization process is produced big influence, and alcohol solvent safety, cheap, environmental protection, be easy to reclaim and recycle.
Embodiment
The comparative example 1
Add 45 gram tetraethyl ammonium hydroxide solution (technical grade, TEAOH 40wt%) in the small-sized one-tenth glue jar of laboratory, (technical grade contains SiO with 16.4 gram white carbon blacks under mechanical stirring
299.9%) adds in the glue jar and dissolve.Add 4.2 gram solid Neutral ammonium fluorides (analytical pure, 〉=96%) then in the gained feed liquid, high degree of agitation forms the high rigidity gel after about 10 minutes, stir and be forced to stop.The mol ratio of each component is in this gel: SiO
2/ Al
2O
3=∞, (TEA)
2O/SiO
2=0.22, OH
-/ SiO
2=0.45, NH
4F/SiO
2=0.3, H
2O/SiO
2=5.5.Above-mentioned gel is carefully dug out with the stainless steel spoon, and move in the static synthesis reactor of small-sized stainless steel (less than 200 milliliters) in 150 ℃ of following crystallization.Take out cooling after four days, after filtration, washing, 110 ℃ be drying to obtain the beta zeolite powder, its grain size is about the 10-15 micron.
Because above-mentioned gel is becoming glue to solidify suddenly midway, hardness is very big, so this gel is easy to stop up into the pipeline of glue jar in large-scale production, can not carry with equipment such as pumps to be transferred in the synthesis reactor, can not carry out mechanical stirring in crystallization process.Therefore can not be used for industrial production.
Embodiment 1
Add 20 gram dehydrated alcohols and 45 gram tetraethyl ammonium hydroxide solution (technical grade, TEAOH 40wt%) in the small-sized one-tenth glue jar of laboratory successively, (technical grade contains SiO with 16.4 gram white carbon blacks under mechanical stirring then
299.9%) adds in the glue jar and dissolve.Add 4.2 gram solid Neutral ammonium fluorides (analytical pure, 〉=96%) then in the gained feed liquid, high degree of agitation forms gel after about 30 minutes, and gel hardness significantly reduces, and stirring can be carried out.The mol ratio of each component is in this gel: SiO
2/ Al
2O
3=∞, (TEA) O
2/ SiO
2=0.22, OH
-/ SiO
2=0.45, NH
4F/SiO
2=0.3, H
2O/SiO
2=5.5, CH
3CH
2OH/SiO
2=1.59 (moles).Above-mentioned gel is moved in the static synthesis reactor of small-sized stainless steel in 150 ℃ of following crystallization.Take out cooling after 6 days, after filtration, washing, 110 ℃ be drying to obtain the beta zeolite powder, its relative crystallinity is 99%, and grain size is about the 6-9 micron.
Embodiment 2
Repeat embodiment 1, but the consumption of alcohol solvent strengthens, and makes CH
3CH
2OH/SiO
2Molar ratio reaches 5,10,20,30 respectively, and 50,80 and 100.Then the above-mentioned raw materials time lag to 1 that forms gel is between 3 hours, but the gained gel can reach good flowability.Above-mentioned gel is moved in the static synthesis reactor of small-sized stainless steel in 150 ℃ of following crystallization.Cooling is taken out in the back in 10-15 days day, and after filtration, washing, 110 ℃ of dryings all obtain the beta zeolite powder, its relative crystallinity is all above 90%, and grain size is in the 3-10 micrometer range.
Embodiment 3
Add 40 gram dehydrated alcohols and 45 gram tetraethyl ammonium hydroxide solution (technical grade, TEAOH 40wt%) in the small-sized one-tenth glue jar of laboratory successively, (technical grade contains SiO with 16.4 gram white carbon blacks successively under mechanical stirring then
299.9%) adds in the glue jar with 0.245 gram self-control alumina dry glue (contents on dry basis 58%) and dissolve.Add 4.2 gram solid Neutral ammonium fluorides (analytical pure, 〉=96%) then in the gained feed liquid, high degree of agitation forms gel after about 50 minutes, and gel hardness is lower, and stirring can be carried out.The mol ratio of each component is in this gel: SiO
2/ Al
2O
3=300, (TEA) O
2/ SiO
2=0.22, OH
-/ SiO
2=0.45, NH
4F/SiO
2=0.3, H
2O/SiO
2=5.5, CH
3CH
2OH/SiO
2=3.2 (moles).Above-mentioned gel is moved in the static synthesis reactor of small-sized stainless steel in 150 ℃ of following crystallization.Take out cooling after 11 days, after filtration, washing, 110 ℃ be drying to obtain the beta zeolite powder, its relative crystallinity is 95%, and grain size is about 5 microns.
Embodiment 4
Repeat embodiment 3, but increase the aluminium hydroxide amount that feeds intake, make SiO
2/ Al
2O
3Than reaching 200 and 100 respectively.Then the hardness of above-mentioned gel is also relatively low, can stir.Above-mentioned gel is moved in the static synthesis reactor of small-sized stainless steel in 150 ℃ of following crystallization.Take out cooling after 20 days, after filtration, washing, 110 ℃ be drying to obtain the beta zeolite powder, its relative crystallinity is followed successively by 95% and 97%, and grain size is about the 3-6 micron.
Embodiment 5
Repeat embodiment 2, but fixation of C H
3CH
2OH/SiO
2Molar ratio is 10, changes gel by the add-on that changes white carbon black, Neutral ammonium fluoride and forms, and makes OH
-/ SiO
2=0.8, NH
4F/SiO
2=0.5, H
2O/SiO
2=12.Then the hardness of this gel is also relatively low, can stir.Above-mentioned gel is moved in the static synthesis reactor of small-sized stainless steel in 150 ℃ of following crystallization.Take out cooling after 25 days, after filtration, washing, 110 ℃ be drying to obtain the beta zeolite powder, its relative crystallinity is followed successively by 94%, and grain size is about about 5 microns.
Embodiment 6
In 2 cubic metres service water thermal synthesis still, synthesize.At first add in synthesis reactor and add 600 kilograms of dehydrated alcohols and 450 kilograms of tetraethyl ammonium hydroxide solution (technical grade, TEAOH 40wt%) successively, (technical grade contains SiO with 164 kilograms of white carbon blacks under mechanical stirring then
299.9%) adds in the glue jar and dissolve.Add 42 kilograms of solid Neutral ammonium fluorides (analytical pure, 〉=96%) then in the gained feed liquid, high degree of agitation forms gel after about 60 minutes, stirs smoothly.The mol ratio of each component is in this gel: SiO
2/ Al
2O
3=∞, (TEA) O
2/ SiO
2=0.22, OH
-/ SiO
2=0.45, NH
4F/SiO
2=0.3, H
2O/SiO
2=5.5, CH
3CH
2OH/SiO
2=4.8 (moles).With above-mentioned gel in 150 ℃ of following crystallization.Sampling analysis after 14 days, its relative crystallinity are 98%, and grain size is about 10 microns.
Embodiment 7
Repeat embodiment 6, but before adding Neutral ammonium fluoride, also in synthesis reactor, add about 1.8 kilograms of self-control aluminum hydroxide solid elastomers (contents on dry basis 58%), make SiO
2/ Al
2O
3Reach 400.With above-mentioned gel in 150 ℃ of following crystallization.Sampling analysis after 15 days, its relative crystallinity are 94%, and grain size is about the 5-6 micron.
Claims (2)
1, a kind of method of synthesizing high silicon beta zeolite, it is characterized in that, earlier alcohol solvent and TEAOH template solution are joined in the material-compound tank successively by following mol ratio, under agitation add white carbon black and aluminum hydroxide solid elastomer then and mix, in the gained feed liquid, add solid NH again
4F, the mol ratio of each material is:
SiO
2/Al
2O
3＝100-∞，
(TEA)O
2/SiO
2＝0.2-0.4，
OH
-/SiO
2＝0.4-0.8，
NH
4F/SiO
2＝0.25-0.5，
H
2O/SiO
2＝5.0-15，
CH
3CH
2OH/SiO
2＝0.5-100，
Continue to stir up to forming the homogeneous gel mixture, with gel mixture 140-160 ℃ of following mechanical stirring crystallization 2-30 days.
2, the method for a kind of synthesizing high silicon beta zeolite according to claim 1 is characterized in that, described alcohol solvent is industry anhydrous ethanol or contains 95% alcoholic acid industrial spirit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102469831A CN101462738B (en) | 2008-12-26 | 2008-12-26 | Method for synthesizing high silicon beta zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102469831A CN101462738B (en) | 2008-12-26 | 2008-12-26 | Method for synthesizing high silicon beta zeolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101462738A true CN101462738A (en) | 2009-06-24 |
| CN101462738B CN101462738B (en) | 2011-03-02 |
Family
ID=40803564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102469831A Expired - Fee Related CN101462738B (en) | 2008-12-26 | 2008-12-26 | Method for synthesizing high silicon beta zeolite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101462738B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105347359A (en) * | 2015-11-27 | 2016-02-24 | 中国石油大学(北京) | Synthesis and application of zeolite molecular sieve with solid acid contained in porous channels |
| CN107628630A (en) * | 2017-09-21 | 2018-01-26 | 华东师范大学 | A kind of hollow molecular sieves of B ZSM 5 and its preparation method and application |
| CN111747426A (en) * | 2020-06-27 | 2020-10-09 | 上海工程技术大学 | Cheap synthesis method of pure silicon and high-silicon CHA molecular sieve |
| CN113636566A (en) * | 2021-08-05 | 2021-11-12 | 肯特催化材料股份有限公司 | All-silicon Beta molecular sieve synthesis process and all-silicon Beta molecular sieve prepared by same |
-
2008
- 2008-12-26 CN CN2008102469831A patent/CN101462738B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105347359A (en) * | 2015-11-27 | 2016-02-24 | 中国石油大学(北京) | Synthesis and application of zeolite molecular sieve with solid acid contained in porous channels |
| CN107628630A (en) * | 2017-09-21 | 2018-01-26 | 华东师范大学 | A kind of hollow molecular sieves of B ZSM 5 and its preparation method and application |
| CN111747426A (en) * | 2020-06-27 | 2020-10-09 | 上海工程技术大学 | Cheap synthesis method of pure silicon and high-silicon CHA molecular sieve |
| CN113636566A (en) * | 2021-08-05 | 2021-11-12 | 肯特催化材料股份有限公司 | All-silicon Beta molecular sieve synthesis process and all-silicon Beta molecular sieve prepared by same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101462738B (en) | 2011-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101519217B (en) | Preparation method of microcrystal mordenites | |
| AU2020101871A4 (en) | A Method for Preparing ZSM-5 Zeolite by Using Solid wastes | |
| US20160002061A1 (en) | Zsm-5 type molecular sieve synthesis method | |
| CN102211779B (en) | Preparation method of beta zeolite | |
| CN101462738B (en) | Method for synthesizing high silicon beta zeolite | |
| CN101898767B (en) | Synthetic method of high silica ZSM-5 zeolite | |
| CN102491366A (en) | Method for preparing hollow zeolite socony mobil-5 (ZSM-5) nanometer zeolite | |
| CN103539153A (en) | Preparation method of nano hierarchical-pore ZSM-11/ZSM-5 eutectic zeolite | |
| CN102992346A (en) | Seed crystal synthesis method for preparing ZSM-23 molecular sieve | |
| WO2008060647A2 (en) | A process for preparing nano size zeolites | |
| CN107010637B (en) | Method for synthesizing silicon-aluminum MCM-49 zeolite by using crystal seed method with cyclohexylamine as template agent | |
| CN101519216B (en) | Method for synthesizing boron-containing molecular sieve | |
| CN101125663A (en) | Synthesis method for ZSM-34 zeolite | |
| CN103058208B (en) | Preparation method of SAPO-56 molecular sieve | |
| CN105293516A (en) | Method for rapidly preparing ZSM-22 molecular sieve by means of seed crystal | |
| CN106607080A (en) | Catalyst for preparing arene through adopting methyl alcohol as raw material and preparation and application methods thereof | |
| CN103803576A (en) | ZSM-48 molecular sieve with low silica-alumina ratio and preparation method thereof | |
| CN108975352A (en) | A kind of preparation method of nano pure silicone ZSM-5 zeolite | |
| CN101993091B (en) | Method for synthesizing ZSM-5 zeolite | |
| CN103121697B (en) | Pure silicon ANA-type zeolite molecular sieve and preparation method thereof | |
| CN101723395B (en) | Method for preparing double-micropore composite molecular sieve | |
| CN105271287A (en) | Method for preparation of Beta molecular sieve from modified diatomite without organic template | |
| CN104591202B (en) | A kind of hollow P type zeolite and preparation method thereof | |
| CN102757066B (en) | Method for synthesizing B-beta-heteroatom molecular sieve | |
| CN105152181A (en) | Preparation method of all-silicon MTN topology structure molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110302 Termination date: 20211226 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |